Gas separation process using membranes with permeate sweep to remove CO2 from combustion exhaust

ABSTRACT

A gas separation process for treating exhaust gases from combustion processes. The invention involves routing a first portion of the exhaust stream to a carbon dioxide capture step, while simultaneously flowing a second portion of the exhaust gas stream across the feed side of a membrane, flowing a sweep gas stream, usually air, across the permeate side, then passing the permeate/sweep gas back to the combustor.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part and claims the benefit ofU.S. application Ser. No. 15/066,771, filed Mar. 10, 2016, which is adivisional of U.S. application Ser. No. 13/548,827, filed Jul. 13, 2012,which issued Oct. 4, 2016 as U.S. Pat. No. 9,457,313; which is acontinuation-in-part and claims the benefit of both (1) U.S. applicationSer. No. 13/115,726, filed May 25, 2011, which issued Jul. 17, 2012 asU.S. Pat. No. 8,220,248; which is a continuation-in-part and claims thebenefit of U.S. application Ser. No. 13/122,136, filed Mar. 31, 2011,which issued May 15, 2012 as U.S. Pat. No. 8,177,885; which is anational stage application of, and claims the benefit of, PCTApplication No. PCT/US10/02480, filed Sep. 13, 2010; and (2) U.S.application Ser. No. 13/122,136, filed Mar. 31, 2011, which issued May15, 2012 as U.S. Pat. No. 8,177,885; which is a national stageapplication of, and claims the benefit of, PCT Application No.PCT/US10/02480, filed Sep. 13, 2010; the entire contents of all of whichapplications are hereby incorporated by reference.

FIELD OF THE INVENTION

The invention relates to membrane-based gas separation processes, andspecifically to processes using a sweep gas on the permeate side of themembranes to remove carbon dioxide from combustion exhaust gases.

BACKGROUND OF THE INVENTION

Many combustion processes produce flue gases contaminated with carbondioxide that contribute to global warming and environmental damage. Suchgas streams are difficult to treat in ways that are both technically andeconomically practical, and there remains a need for better treatmenttechniques.

Gas separation by means of membranes is a well-established technology.In an industrial setting, a total pressure difference is usually appliedbetween the feed and permeate sides, typically by compressing the feedstream or maintaining the permeate side of the membrane under partialvacuum.

It is known in the literature that a driving force for transmembranepermeation may be supplied by passing a sweep gas across the permeateside of the membranes, thereby lowering the partial pressure of adesired permeant on that side to a level below its partial pressure onthe feed side. In this case, the total pressure on both sides of themembrane may be the same, the total pressure on the permeate side may behigher than on the feed side, or there may be additional driving forceprovided by keeping the total feed pressure higher than the totalpermeate pressure.

Using a sweep gas has most commonly been proposed in connection with airseparation to make nitrogen or oxygen-enriched air, or with dehydration.Examples of patents that teach the use of a sweep gas on the permeateside to facilitate air separation include U.S. Pat. Nos. 5,240,471;5,500,036; and 6,478,852. Examples of patents that teach the use of asweep gas in a dehydration process include U.S. Pat. Nos. 4,931,070;4,981,498 and 5,641,337.

Configuring the flow path within the membrane module so that the feedgas and sweep stream flow, as far as possible, countercurrent to eachother is also known, and taught, for example in U.S. Pat. Nos. 5,681,433and 5,843,209.

The use of a process including a membrane separation step operated insweep mode for treating flue gas to remove carbon dioxide is taught inco-owned U.S. Pat. No. 7,964,020.

SUMMARY OF THE INVENTION

The invention is a process involving membrane-based gas separation forcontrolling carbon dioxide emissions from combustion processes in whichcarbon dioxide emissions are so controlled.

Combustion exhaust streams or off-gases are typically referred to asflue gas, and arise in large quantities from different types ofcombustion apparatuses, including ovens, furnaces, boilers, gasturbines, and gas-powered or diesel-powered engines. In particular,power plants generate enormous amounts of flue gas. For example, amodestly sized 100 megawatt power plant may produce over 300 MMscfd offlue gas.

The major components of combustion exhaust gases are normally nitrogen,carbon dioxide, and water vapor. Other components that may be present,typically only in small amounts, include oxygen, hydrogen, SO_(x),NO_(x), and unburnt hydrocarbons. Syngas may also contain heavy metals,such as mercury. The carbon dioxide concentration in the flue gas isgenerally up to about 20 vol %.

In addition to gaseous components, combustion flue gas—depending on thefuel used—may contain suspended particulate matter in the form of flyash and soot. This material is usually removed by several stages offiltration before the gas is sent to the stack. It is assumed hereinthat the flue gas has already been treated in this way, if desired,prior to carrying out the processes of the invention.

The process of the invention involves treating the exhaust or flue gasto remove carbon dioxide. In preferred embodiments, the carbon dioxidelevel of the exhaust gas is reduced to as low as 5 vol % or less.Discharge of such a stream to the environment is much less damaging thandischarge of the untreated exhaust.

The combustion process from which the exhaust is drawn may be of anytype. The fuel may be a fossil fuel, such as coal, oil or natural gas,or may be from any other source, including but not limited to syngas,refinery fuel gas, blast furnace off-gas, landfill gas, biomass, orother combustible waste. The fuel may be combusted by mixing with air,oxygen-enriched air, or pure oxygen. For processes that combustmethane-containing gases, it is often a requirement that the gas beingburnt should be mixed with a diluent gas to control the flametemperature of the combustor. Typically, the diluent is excess air,steam, or nitrogen, or it may be provided by partial recycling of theflue gas exhaust. In natural gas combustion, the volume of diluent maybe equal or greater than the volume of air required for stoichiometriccombustion of the gas.

After the combustion step itself, a first portion of the flue gas issubjected to a carbon dioxide capture step. This capture step removes aportion of the carbon dioxide from the emissions stream, and preferablyprovides it in the form of a concentrated stream, such as greater than60, 70, or 80 vol % carbon dioxide, and most preferably as asupercritical fluid or liquid high purity product. The concentratedproduct stream may be sent for sequestration, or for any other use.

The capture step may utilize any separation technology suitable forrecovering carbon dioxide from a stream of the exhaust gasconcentration. Preferred technologies are absorption, such as aminescrubbing or chilled ammonia sorption, membrane separation, andcondensation.

The off-gas stream from the capture step still contains carbon dioxide,but normally at a lower concentration than the raw exhaust stream.Typically, this concentration will be less than half that of the feed.

A second portion of the flue gas is sent for treatment in a sweep-basedmembrane separation unit. The unit contains membranes selectivelypermeable to carbon dioxide over nitrogen, and to carbon dioxide overoxygen. It is preferred that the membrane provide a carbon dioxidepermeance of at least about 300 gpu, more preferably at least about 500gpu, and most preferably at least about 1,000 gpu under the operatingconditions of the process. A carbon dioxide/nitrogen selectivity of atleast about 10, or more preferably 20, under the operating conditions ofthe process is also desirable.

The off-gas flows across the feed side of the membranes, and a sweep gasof air, oxygen-enriched air, or oxygen flows across the permeate side,to provide or augment the driving force for transmembrane permeation.

The sweep stream picks up the preferentially permeating carbon dioxide.The combined sweep/permeate stream is then withdrawn from the membraneunit and is returned to the combustor to form at least part of the air,oxygen-enriched air, or oxygen feed to the combustion step.

By using the oxygen-containing stream destined for the combustor assweep gas, the membrane separation step is carried out in a veryefficient manner, and without introducing any additional unwantedcomponents into the combustion zone.

The process is particularly useful in applications that areenergy-sensitive, as is almost always the case when the very largestreams from power plants and the like are to be processed.

The process is also particularly useful in separations that arepressure-ratio limited, as will be explained in more detail below.

The membrane separation step may be carried out using one or moreindividual membrane modules. Any modules capable of operating underpermeate sweep conditions may be used. Preferably, the modules take theform of hollow-fiber modules, plate-and-frame modules, or spiral-woundmodules. All three module types are known, and their configuration andoperation in sweep, including counterflow sweep modes, is described inthe literature.

The process may use one membrane module, but in most cases, theseparation will use multiple membrane modules arranged in series orparallel flow arrangements as is well known in the art. Any number ofmembrane modules may be used.

The process may be augmented by operating the membrane unit with highertotal pressure on the feed side than on the permeate side, therebyincreasing the transmembrane driving force for permeation.

It is highly preferred that the feed gas flow direction across themembrane on the feed side and the sweep gas flow direction across themembrane on the permeate side are substantially countercurrent to eachother. In the alternative, the relative flow directions may besubstantially crosscurrent, or less preferred, cocurrent.

The residue stream is reduced in carbon dioxide content to less thanabout 5 vol %. This stream is typically, although not necessarily,discharged to the environment. The substantial reduction of the carbondioxide content in the raw exhaust greatly reduces the environmentalimpact of discharging the stream.

The invention, in a basic embodiment, includes three steps: a combustionstep, a carbon dioxide capture step, and a sweep-based membraneseparation step, where the carbon dioxide capture step and thesweep-based membrane separation step are performed in parallel. That is,a portion of the exhaust stream from the combustion process is routed toa carbon dioxide capture step, and the other portion is routed to asweep-based membrane separation step. Thus, in one embodiment, theprocess of the invention comprises the following steps:

-   -   (a) performing a combustion process by combusting a mixture        comprising a gaseous fuel and air, oxygen-enriched air, or        oxygen, thereby creating an exhaust stream comprising carbon        dioxide and nitrogen;    -   (b) performing a carbon dioxide capture step to remove a portion        of carbon dioxide in concentrated form from a first portion of        the exhaust stream;    -   (c) providing a membrane having a feed side and a permeate side,        and being selectively permeable to carbon dioxide over nitrogen        and to carbon dioxide over oxygen;    -   (d) passing a second portion of the exhaust stream across the        feed side;    -   (e) passing air, oxygen-enriched air, or oxygen as a sweep        stream across the permeate side;    -   (f) withdrawing from the feed side a carbon dioxide-depleted        vent stream;    -   (g) withdrawing from the permeate side a permeate stream        comprising oxygen and carbon dioxide;    -   (h) passing the permeate stream to step (a) as at least part of        the air, oxygen-enriched air, or oxygen used in step (a).

An objective of the invention is to substantially increase theconcentration of carbon dioxide in the exhaust stream from the combustoror boiler, so that the portion of the exhaust stream that is sent to thecarbon dioxide capture step can itself be concentrated and captured moreefficiently than would otherwise be possible. This is achieved byreturning the carbon dioxide-enriched permeate stream from the membraneseparation step to the combustor. The exhaust stream preferablycomprises at least 15 vol % CO₂.

If the gas needs to be transported to reach the equipment that carriesout the carbon dioxide capture step, such as an amine or cryogenicplant, transportation of the carbon dioxide enriched exhaust gas is farsimpler and less costly than transporting low concentration raw flue gasfrom a conventional power plant. Typically, the amount of gas that mustbe pipelined or otherwise transported to the carbon dioxide captureplant is reduced several fold, such as to 50%, 30%, or even 25% or lessof the amount that would need to be sent if the membrane separation stepwere absent. This is a significant benefit of the invention.

The portion of the exhaust stream that is sent to the carbon dioxidecapture step (i.e., the “first portion”) preferably comprises betweenabout 10 vol % and about 66 vol %; more preferably, between about 20 vol% and about 50 vol %; and, most preferably, between about 25 vol % andabout 35 vol %, of the total exhaust stream. This can also be expressedas a split ratio, where the ratio defines the relative proportions ofthe flue gas sent to the carbon dioxide capture step and the membraneseparation step. In general, we prefer to operate with a split ratio ofbetween 1:1 and 1:5.

The carbon dioxide capture step preferably comprises at least oneprocess selected from the group consisting of absorption, adsorption,liquefaction, and membrane separation, and most preferably comprisesmembrane separation or cryogenic condensation.

The other (“second”) portion of the exhaust stream is sent to asweep-based membrane separation step. The second portion of the exhauststream may be sent to the membrane unit without compression, or may becompressed. Slight compression to a pressure from between about 1.5 barup to about 5 bar, such as 2 bar, is preferred. The sweep streampreferably follows a sweep flow direction across the permeate side, theoff-gas stream follows a feed flow direction across the feed side, andthe sweep flow direction is substantially countercurrent to the feedflow direction. The membrane preferably exhibits a carbon dioxidepermeance of at least 500 gpu, and a selectivity in favor of carbondioxide over nitrogen of at least 10, under process operatingconditions.

Another objective of the invention is to minimize the amount of CO₂ inthe vent stream, which is often released directly to the environment. Assuch, the vent stream preferably comprises less than 5 vol % CO₂.

In certain embodiments, the exhaust gas is compressed before beingtreated in the carbon capture and sweep-based membrane separation steps.To provide the power necessary to drive the compressor, the compressormay be mechanically linked to an expander unit, such as aturbo-expander, in which the treated exhaust gases pass through beforebeing released into the environment. In this way, much of the energythat is used to compress the exhaust gas before treatment is recoveredin the expansion step from the treated gases. Thus, in a furtherembodiment, the process of the invention comprises the following steps:

-   -   (a) combusting a mixture comprising a fuel and air,        oxygen-enriched air, or oxygen in a combustion apparatus,        thereby creating an exhaust stream comprising carbon dioxide and        nitrogen;    -   (b) routing the exhaust stream to a compression apparatus to        compress the exhaust stream, thereby producing a compressed        stream;    -   (c) separating a first portion of the compressed stream in a        carbon dioxide capture unit adapted to selectively remove carbon        dioxide, thereby producing a carbon dioxide-enriched stream and        a carbon dioxide-depleted off-gas stream;    -   (d) providing a membrane having a feed side and a permeate side,        and being selectively permeable to carbon dioxide over nitrogen        and to carbon dioxide over oxygen;    -   (e) passing a second portion of the compressed stream across the        feed side;    -   (f) passing air, oxygen-enriched air, or oxygen as a sweep        stream across the permeate side;    -   (g) withdrawing from the feed side a carbon dioxide-depleted        residue stream;    -   (h) withdrawing from the permeate side a permeate stream        comprising oxygen and carbon dioxide;    -   (i) passing the permeate stream to step (a) as at least part of        the air, oxygen-enriched air, or oxygen used in step (a); and    -   (j) routing at least one of the carbon dioxide-depleted off-gas        stream from step (c) or the carbon dioxide-depleted residue        stream from step (g) as a part of a working gas stream to an        expander unit, and operating the expander unit, thereby        generating power and producing a vent stream.

The cost of compression is typically lower when the gas being compressedis cool. Thus, it is preferred that the exhaust stream is cooled priorto being sent to the compression apparatus. Cooling may be performed inany manner, and in one or more sub-steps, including, but not limited to,simple air or water cooling, heat exchange against other on-site processstreams, chilling by external refrigerants, cooling in a condensationstep, and any combinations of these. Likewise, the energy recovered inthe expander unit is higher when the gas being expanded is warm. Warmingmay be accomplished in any way, preferably by heat exchange against thehot exhaust stream.

In certain aspects, depending on operating conditions, only one of thecarbon dioxide-depleted streams for step (c) or step (g) of the aboveembodiment may be sent to the expander unit while the other streamundergoes further treatment, is recycled back to the process, orreleased into the environment. In other aspects, both streams may makeup part of the working gas stream that is eventually sent to theexpander unit.

The capture step in this embodiment may utilize any separationtechnology suitable for recovering carbon dioxide from a stream of theexhaust gas concentration as discussed above.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic drawing of a flow scheme for a basic embodiment ofthe invention as it relates to a typical process for combustion of agaseous fuel.

FIG. 2 is a schematic drawing of a flow scheme for a combustion processthat does not include a sweep-based membrane separation step (not inaccordance with the invention).

FIG. 3 is a schematic drawing of a flow scheme for a combustion processthat does not include a sweep-based membrane separation step, but inwhich a portion of the combustion exhaust stream is routed back to thecombustor (not in accordance with the invention).

FIG. 4 is a schematic drawing of a flow scheme for a combustion processin which a portion of the combustion exhaust stream is routed to anamine scrubbing plant and the other portion is routed back to thecombustor (not in accordance with the invention).

FIG. 5 is a schematic drawing of a flow scheme for a combustion processin which the combustion exhaust stream is compressed and a portion ofthe compressed stream is routed to an amine scrubbing plant, and theother portion is routed back to the combustor. The compressednitrogen-rich exhaust stream from the amine scrubbing process is thenrouted back to provide power to the compressor (not in accordance withthe invention).

FIG. 6 is a schematic drawing of a flow scheme for a combustion processin accordance with the invention in which the combustion exhaust streamis compressed and a portion of the compressed stream is routed to anamine scrubbing plant, and the other portion is routed to a sweep-basedmembrane separation step. The sweep stream fiom the membrane separationstep is then routed back to the combustor.

FIG. 7 is a schematic drawing of a flow scheme for a variant of theprocess of FIG. 6, in which membrane separation is used in the carbondioxide capture step rather than an amine scrubbing plant.

FIG. 8 is a schematic drawing of a flow scheme for a variant of theprocess of FIG. 7, in which two membrane separation steps are used inthe carbon dioxide capture step.

DETAILED DESCRIPTION OF THE INVENTION

Gas percentages given herein are by volume unless stated otherwise.

Pressures as given herein are in bar absolute unless stated otherwise.

The terms exhaust gas, off-gas, flue gas, and emissions stream are usedinterchangeably herein.

The terms natural gas, syngas, and fuel are used interchangeably herein.

The invention is a process for controlling carbon dioxide emissions fromcombustion processes by membrane-based gas separation, and combustionprocesses including such gas separation. The invention incorporatesthree unit operations: a combustion step, a carbon dioxide capture step,and a sweep-based membrane separation step, where the carbon dioxidecapture step and the sweep-based membrane separation step are performedin parallel. A portion of the exhaust stream from the combustion processis routed to the carbon dioxide capture step, and the other portion isrouted to the sweep-based membrane separation step.

In certain aspects, the process is expected to be particularly usefulfor treating flue or exhaust gas from gas-fired power plants, such ascombined cycle plants, which typically use natural gas as fuel, and IGCC(Integrated Gasification Combined Cycle) plants, which use syngas,typically made by gasifying coal, as fuel. In a conventional combinedcycle plant, for example, it is common to dilute the mixture of gases inthe combustion chamber by feeding an excess of air, such as twice theflow needed to satisfy the stoichiometric ratio for the combustionreactions. The excess air does not take part in the reactions, butdilutes the combustion gases, thereby moderating the exhaust gastemperature. As an alternative or in addition to feeding excess air, aportion of the exhaust gas itself is sometimes returned to thecombustor. In some IGCC plants, where the gasifier uses an oxygen feed,nitrogen produced as a co-product of oxygen production is used as adiluent for the fuel gas being combusted.

In a combined cycle power plant, for example, the gaseous fuel iscombusted to produce a hot gas that is used to drive a gas turbine,producing power. The exhaust gas from the combustor is still very hotand so is used to boil water, producing steam that can then drive asteam turbine. The exhaust gas from this step is the flue gas to betreated in the process of the invention.

In some similar processes, the gaseous fuel is burnt to produce heat,for example, in a methane gas reformer furnace. The hot exhaust gas fromthe combustor is often cooled by running it through a recuperatorcounter to the incoming air stream to the combustor. In this case, theexhaust gas from the recuperator is the flue gas to be treated in theprocess of the invention.

A simple flow scheme for one embodiment of the invention is shown inFIG. 1. Fuel stream 102 and air, oxygen-enriched air, or oxygen stream104 are introduced into combustion step or zone 112. Stream 104 is madeup of sweep stream 103 (discussed below) and, optionally, additional airor oxygen supply stream 115. The ratios of fuel and air may be adjustedas convenient in accordance with known combustion principles, such as tomeet the temperature control needs of a combined cycle operation, asmentioned above. The oxygen with which the fuel is combusted may besupplied in the form of high purity oxygen, oxygen-enriched air, normalair, or any other suitable oxygen-containing mixture. The process may becarried out at atmospheric pressure or at elevated pressure.

Combustion exhaust stream 105—preferably containing at least 15 vol %;more preferably, at least 20 vol %; and, most preferably, at least 25vol %, carbon dioxide—is withdrawn. This stream usually contains atleast carbon dioxide, water vapor, nitrogen, and oxygen. Combustionexhaust stream 105 is optionally but typically routed through acondenser 114, where water 110 is knocked out of the stream. Thedehydrated exhaust stream 106 is then routed through a splitter 116,where it is divided in a desired ratio into a first portion 107 and asecond portion 108.

The first portion 107 of exhaust stream 106 is routed to a carbondioxide capture step 113. The carbon dioxide capture step may be carriedout using any technology or combination of technologies that can createa concentrated carbon dioxide stream from the exhaust stream. Thecapture step yields a concentrated carbon dioxide product stream 117preferably containing greater than 60, 70, or 80 vol % carbon dioxide ormore. This stream may be in the gas or liquid phase, or may be asupercritical fluid. The concentrated stream 117 may be sent for furtherprocessing in a sequestration step (not shown) to yield a liquid carbondioxide product, for example, but alternatively may be used or disposedof in any other appropriate way. The off-gas stream, 119, usuallycontains mostly nitrogen and can be released to the environment.

The carbon dioxide capture step 113 may be carried out using membrane ornon-membrane technology, and may involve one or more than one type ofseparation procedure. In the event that membrane technology is used inwhole or part for this step, the capture step 113 remains a discreteunit operation separate from the simultaneous sweep-based membraneseparation step 111.

Representative methods that may be used to capture carbon dioxide inthis step include, but are not limited to, physical or chemicalsorption, membrane separation, compression/low temperature condensation,adsorption, or any other known technology. Preferred technologies areabsorption, such as amine scrubbing or chilled ammonia sorption,condensation, membrane separation, cryogenic condensation, andcombinations of these. The benefit of using the described technology isthat the carbon dioxide of the gas being treated in the capture step issubstantially enriched compared to exhaust gas produced without themembrane unit. The smaller volume and higher carbon dioxide content ofthe gas significantly reduces the cost of the carbon dioxide capturestep and processes previously uneconomical with low concentration carbondioxide streams can be considered; for example, physical absorption,cryogenic, or membrane separation.

If membrane separation is used for the carbon dioxide capture step, itis preferred to use two or more membrane separation steps, as it isdifficult to reach a high carbon dioxide concentration in the permeatestream without using multiple membrane stages. An example of athree-stage membrane unit for carbon dioxide recovery from natural gasstreams is given in U.S. Pat. No. 6,648,944. Examples of multiplemembrane separations steps used as a carbon dioxide capture step aregiven in U.S. Pat. No. 7,964,020.

Low-temperature or cryogenic condensation and absorption into an aminesolution are the most common methods in current industrial use forcapturing carbon dioxide and need no detailed description herein. Eithermethod is well-suited for use in the present invention. Methods ofrecovering liquid carbon dioxide by cryogenic condensation ordistillation are well known in the art. A preferred process is thewell-known Ryan-Holmes process, in which a light hydrocarbon liquid orliquid mixture is added to the column to prevent formation of carbondioxide solids or azeotropes in the column. Various specific techniquesfor carrying out low temperature condensation are taught, for example inU.S. Pat. Nos. 4,371,381; 4,923,493; 5,233,837. The Ryan-Holmes processis taught in U.S. Pat. Nos. 4,350,511 and 4,462,814, for example.

Methods of recovering carbon dioxide by absorption are also commonlyused. In brief, these methods involve absorbing the carbon dioxide intoa sorbent solution by physical or chemical interaction, then strippingthe gas from the solution and recirculating the regenerated sorbent.Various sorbents may be used; most commonly, the sorbent is amine-basedand may include a single alkanolamine or a mix of amines. Other sorbentsthat may be used include chilled ammonia, as in the Alstom process, orother specialized proprietary solvents.

The sorbent solution may be regenerated by steam stripping, and thecarbon dioxide recovered from the stripping vapor by cooling andcondensing the water. A representative process of this type that may beused is the Fluor Daniel Econamine FG™ process, which uses amonoethanolamine (MEA) based sorbent system. Very detailed descriptionsof such processes can be found in the literature, for example in GasPurification, A. Kohl and R. Nielsen (Fifth Edition, Gulf PublishingCo., Houston, Tex., 1997), pages 1188-1237.

Two or more different separation technologies may also be combined inthis step; membrane separation may be combined with cryogeniccondensation, either upstream or downstream of the condensation step,for example, or gas released in the stripping step of the absorptionprocess may be liquefied by condensation. Examples of such combinedprocesses are taught in U.S. Pat. Nos. 4,639,257; 4,990,168; 5,233,837;and 6,085,549, for example, all of which are incorporated herein byreference.

Concurrently with the carbon dioxide capture step, a second portion 108of combustion exhaust stream 106 is sent for treatment in sweep-basedmembrane separation step or unit 111. The membrane separation unit 111contains membranes 118 that exhibit high permeance for carbon dioxide,as well as high selectivity for carbon dioxide over nitrogen.

Any membrane with suitable performance properties may be used. Manypolymeric materials, especially elastomeric materials, are verypermeable to carbon dioxide. Preferred membranes for separating carbondioxide from nitrogen or other inert gases have a selective layer basedon a polyether. A number of membranes are known to have high carbondioxide/nitrogen selectivity, such as 30, 40, 50, or above, although theselectivity may be much lower under actual operating conditions. Arepresentative preferred material for the selective layer is Pebax®, apolyamide-polyether block copolymer material described in detail in U.S.Pat. No. 4,963,165. We have found that membranes using Pebax® as theselective polymer can maintain a selectivity of 10 or greater underprocess conditions.

The membrane may take the form of a homogeneous film, an integralasymmetric membrane, a multilayer composite membrane, a membraneincorporating a gel or liquid layer or particulates, or any other formknown in the art. If elastomeric membranes are used, the preferred formis a composite membrane including a microporous support layer formechanical strength and a rubbery coating layer that is responsible forthe separation properties.

The membranes may be manufactured as flat sheets or as fibers and housedin any convenient module form, including spiral-wound modules,plate-and-frame modules, and potted hollow-fiber modules. The making ofall these types of membranes and modules is well known in the art. Toprovide countercurrent flow of the sweep gas stream, the modulespreferably take the form of hollow-fiber modules, plate-and-framemodules, or spiral-wound modules.

Flat-sheet membranes in spiral-wound modules is the most preferredchoice for the membrane/module configuration. A number of designs thatenable spiral-wound modules to be used in counterflow mode with orwithout sweep on the permeate side have been devised. A representativeexample is described in U.S. Pat. No. 5,034,126, to Dow Chemical.

Membrane step or unit 111 may contain a single membrane module or bankof membrane modules or an array of modules. A single unit or stagecontaining one or a bank of membrane modules is adequate for manyapplications. If the residue stream requires further purification, itmay be passed to a second bank of membrane modules for a secondprocessing step. If the permeate stream requires further concentration,it may be passed to a second bank of membrane modules for a second-stagetreatment. Such multi-stage or multi-step processes, and variantsthereof, will be familiar to those of skill in the art, who willappreciate that the membrane separation step may be configured in manypossible ways, including single-stage, multistage, multistep, or morecomplicated arrays of two or more units in serial or cascadearrangements.

Although the membrane modules are typically arranged horizontally, avertical configuration may in some cases be preferred in order to reducethe risk of deposition of particulates on the membrane feed surface.

The separation of components achieved by the membrane unit depends notonly on the selectivity of the membrane for the components to beseparated, but also on the pressure ratio. By pressure ratio, we meanthe ratio of total feed pressure/total permeate pressure. In pressuredriven processes, it can be shown mathematically that the enrichment ofa component (that is, the ratio of component permeate partialpressure/component feed partial pressure) can never be greater than thepressure ratio. This relationship is true, irrespective of how high theselectivity of the membrane may be.

Further, the mathematical relationship between pressure ratio andselectivity predicts that whichever property is numerically smaller willdominate the separation. Thus, if the numerical value of the pressureratio is much higher than the selectivity, then the separationachievable in the process will not be limited by the pressure ratio, butwill depend on the selectivity capability of the membranes. Conversely,if the membrane selectivity is numerically very much higher than thepressure ratio, the pressure ratio will limit the separation. In thiscase, the permeate concentration becomes essentially independent of themembrane selectivity and is determined by the pressure ratio alone.

High pressure ratios can be achieved by compressing the feed gas to ahigh pressure or by using vacuum pumps to create a lowered pressure onthe permeate side, or a combination of both. However, the higher theselectivity, the more costly in capital and energy it becomes to achievea pressure ratio numerically comparable with or greater than theselectivity.

From the above, it can be seen that pressure-driven processes usingmembranes of high selectivity for the components to be separated arelikely to be pressure ratio-limited. For example, a process in which amembrane selectivity of 40, 50, or above is possible (such as is thecase for many carbon dioxide/nitrogen separations) will only be able totake advantage of the high selectivity if the pressure ratio is ofcomparable or greater magnitude.

The inventors have overcome this problem and made it possible to utilizemore of the intrinsic selective capability of the membrane by dilutingthe permeate with the sweep gas, stream 101, thereby preventing thepermeate side concentration building up to a limiting level.

This mode of operation can be used with a pressure ratio of 1, that is,with no total pressure difference between the feed and permeate sides,with a pressure ratio less than 1, that is, with a higher total pressureon the permeate side than on the feed side, or with a relatively modestpressure ratio of less than 10 or less than 5, for example.

The driving force for transmembrane permeation is supplied by loweringthe partial pressure of the desired permeant on the permeate to a levelbelow its partial pressure on the feed side. The use of the sweep gasstream 101 maintains a low carbon dioxide partial pressure on thepermeate side, thereby providing driving force.

The partial pressure on the permeate side may be controlled by adjustingthe flow rate of the sweep stream to a desired value. In principle, theratio of sweep gas flow to feed gas flow may be any value that providesthe desired results, although the ratio sweep gas flow:feed gas flowwill seldom be less than 0.5 or greater than 10. High ratios (that is,high sweep flow rate) achieve maximum carbon dioxide removal from thefeed, but a comparatively carbon dioxide dilute permeate stream (thatis, comparatively low carbon dioxide enrichment in the sweep gas exitingthe modules). Low ratios (that is, low sweep flow rate) achieve highconcentrations of carbon dioxide in the permeate, but relatively lowlevels of carbon dioxide removal from the feed.

Use of a too low sweep rate may provide insufficient driving force for agood separation, and use of an overly high sweep flow rate may lead topressure drop or other problems on the permeate side, or may adverselyaffect the stoichiometry in the reaction vessel. Typically andpreferably, the flow rate of the sweep stream should be between about50% and 300% of the flow rate of the membrane feed stream; morepreferably, between about 80% and 200%; and, most preferably, betweenabout 80% and 150%.

The total gas pressures on each side of the membrane may be the same ordifferent, and each may be above or below atmospheric pressure. Asmentioned above, if the pressures are about the same, the entire drivingforce is provided by the sweep mode operation.

In most cases, however, flue gas is available at atmospheric pressure,and the volumes of the streams involved are so large that it is notpreferred to use either significant compression on the feed side orvacuum on the permeate side. However, slight compression, such as fromatmospheric to 2 or 3 bar, can be helpful and can provide part of atotal carbon dioxide capture and recovery process that is relativelyenergy efficient, as shown in the examples below. Further, if thecombustion step is performed at high pressure, such as at 5 bar, 10 baror even 20 bar, as in a combined cycle plant, for example, then processdesigns that involve compressing the exhaust gas to relatively higherpressures, such as 10 bar, can be contemplated. These designs enable theportion of gas sent to the carbon dioxide capture step to be sent atpressure, and enable the membrane separation step to be operated with arelatively high pressure on the permeate side, thereby reducing theamount of compression needed before the permeate/sweep stream enters thecombustor.

Returning again to FIG. 1, the second portion 108 of combustion exhauststream 106 flows across the feed side of the membranes; a sweep gas ofair, oxygen-enriched air, or oxygen stream 101, flows across thepermeate side. The sweep stream picks up the preferentially permeatingcarbon dioxide, and the resulting permeate stream 103 is withdrawn fromthe membrane unit and is combined with stream 115 to form the air oroxygen feed 104 to the combustor. In the alternative, stream 115 may beomitted and the entirety of the oxygen-containing feed to the combustormay be provided by the permeate stream 103.

As discussed previously, one of the additional benefits of using thecombustion air or oxygen supply as the permeate sweep is that thepermeating carbon dioxide removed into the sweep gas is recycled to thecombustion chamber. This increases the carbon dioxide concentration inthe exhaust gas leaving the combustor, facilitating the downstreamcapture of carbon dioxide.

The residue stream 109 resulting from the membrane sweep step 111 isreduced in carbon dioxide content to less than about 5 vol %, morepreferably, to less than 3 vol %; and, most preferably, to less than 2vol %. The residue stream 109 is typically discharged to the environmentas treated flue gas.

The proportions of the flue gas that are directed to the carbon dioxidecapture step and the sweep-based membrane separation step may beadjusted in conjunction with other operating parameters to tailor theprocesses of the invention to specific circumstances.

One of the goals of the process is to increase the carbon dioxideconcentration in the feed stream to the carbon dioxide capture step,because many capture technologies, such as amine scrubbing and cryogeniccondensation, have capital and/or operating costs that scale with theconcentration of the component to be captured. The membrane separationstep preferentially permeates carbon dioxide and returns it to thecombustor, thereby forming a loop between the combustor and the membraneunit in which the carbon dioxide concentration can build up.

The more exhaust gas that is directed to the membrane unit, in otherwords, the smaller the split ratio, the greater is the potential toincrease the carbon dioxide concentration in the loop. However, theamount of membrane area needed will increase in proportion to the volumeflow of gas directed to the membrane unit. Furthermore, most membranematerials have slight selectivity for oxygen over nitrogen, so a littleoxygen from the air sweep stream will tend to counter-permeate to thefeed side of the membranes and be lost in the residue stream. Inconsequence, the concentration of oxygen in the combustor may drop,giving rise to the possibility of incomplete combustion or otherproblems. As an indication that the combustion step is still beingprovided with an adequate supply of oxygen, we prefer the process to beoperated so as to provide an oxygen concentration of at least about 3vol % in the exhaust gas stream (based on the composition after waterremoval.)

We have discovered that trade-offs exist between the degree of carbondioxide enrichment that can be obtained by the membrane separationsteps, the amount of oxygen lost into the residue stream, and themembrane area and compression requirements to operate the membraneseparation step.

In light of these trade-offs, we believe that it is preferable tooperate the process at a split ratio of between 1:9 and 2:1; morepreferably, between 1:4 and 1:1; and, most preferably, between 1:2 and1:1. A split ratio of 1:1 means that splitter, 116, divides the totalflue gas flow from the combustor into two equal portions by volume. Asplit ratio of 1:9 means that the splitter directs one volume to thecarbon dioxide capture step and nine volumes to the sweep-based membraneseparation step. In other words, in the 1:1 case, 50 vol % passes to thecarbon dioxide capture step, and in the 1:9 case, 10 vol % passes to thecarbon dioxide capture step. To provide a good balance of efficiency andcosts, we have discovered that the process should most preferably beoperated at a split ratio of between about 1:3 and 1:6; that is, withabout 15-25 vol % of the flue gas being sent from the combustor to thecarbon dioxide capture step.

The invention is now further described by the following examples, whichare intended to be illustrative of the invention, but are not intendedto limit the scope or underlying principles in any way.

EXAMPLES Example 1 Bases of Calculations for other Examples

(a) Membrane permeation experiments: The following calculations wereperformed using a composite membrane having a polyether-based selectivelayer with the properties shown in Table 1.

TABLE 1 Gas Permeance (gpu)* CO₂/Gas Selectivity Carbon dioxide 1,000  — Nitrogen 30 33 Oxygen 60 17 Hydrogen 100  10 Water 5,000**  — *Gaspermeation unit; 1 gpu = 1 × 10⁻⁶ cm³(STP)/cm² · s · cmHg **Estimated,not measured

(b) Calculation methodology: All calculations were performed using amodeling program, ChemCad 5.6 (ChemStations, Inc., Houston, Tex.),containing code for the membrane operation developed by MTR'sengineering group. For the calculations, all compressors and vacuumpumps were assumed to be between 75-85% efficient. In each case, themodeling calculation was performed to achieve 90% recovery of carbondioxide from the flue gas stream, except for Examples 8 and 9.

(c) “No membrane” example: A computer calculation was performed todetermine the chemical composition of untreated exhaust gas from anatural gas combustion process, such as might occur in a 500 MW combinedcycle power plant using about twice the stoichiometric ratio of air tofuel. FIG. 2 is a schematic drawing of a flow scheme for a combustionprocess that does not include a sweep-based membrane separation step.

Referring to FIG. 2, natural gas stream 202 and air stream 201 areintroduced into combustion step or zone 203. (The combustion step andthe oxygen with which the fuel is combined are as described in theDetailed Description, above). The combustion step was assumed to becarried out at 20 bar, a typical representative value for a combinedcycle power plant. Incoming air at atmospheric pressure would typicallybe compressed to 20 bar in a compression step (not shown in the figure).

Combustion exhaust stream 204 is withdrawn, then routed through acondenser 207, where water 205 is knocked out of the stream. Thechemical composition of the resulting untreated gas stream 206 was thencalculated. The results of this calculation are shown in Table 2, below.

TABLE 2 Stream Gas to Condenser Combustor Air Stream Knockout ExhaustGas Parameter (202) (201) (205) (206) Total Flow (kg/h) 66,000 2,688,000113,280 2,640,720 Temperature 25 25 30 30 (° C.) Pressure (bar) 20 1.01.0 1.0 Component (vol %) Methane 100.0 0 0 0 Oxygen 0 79.0 0 12.5Nitrogen 0 21.0 0 80.9 Carbon Dioxide 0 0 0 4.5 Water 0 0 100 2.1

After the water vapor in the stream is condensed, the carbon dioxideconcentration in the combustion exhaust stream is 4.5 vol %, which istoo low to enable the stream to be treated economically by traditionalmeans, such as absorption or low-temperature condensation. Emitting sucha flue gas stream from a power plant would release about 3,000 ton/dayof carbon dioxide to the atmosphere.

Example 2 Combustion Process with Partial Flue Gas Recycle and NoMembrane Step (not in Accordance with the Invention)

A computer calculation was performed to determine the chemicalcomposition of untreated exhaust gas from a natural gas combustionprocess. The process differed from the base-case calculation of Example1 in that the intake of air was reduced to about half that of Example 1,and the remainder of the gas required for temperature and flow controlin the combustor was assumed to be provided by recirculating a portionof the combustion exhaust gas to the combustor inlet, as is commonlydone. FIG. 3 is a schematic drawing of a flow scheme for such acombustion process.

Referring to FIG. 3, natural gas stream 302 and air stream 304 areintroduced into combustion step or zone 312. Stream 304 is made up ofrecycled exhaust stream 307 and additional air or oxygen supply stream301.

Combustion exhaust stream 305 is withdrawn, then routed through acondenser 314, where water 310 is knocked out of the stream. Thedehydrated exhaust stream 306 is then routed through a splitter 316,where it is divided into a first portion 307 and a second portion 308.In this example, the first portion 307 and the second portion 308 werein a ratio of 1:1. The first portion 307 of the dehydrated exhauststream is routed back to the combustor 312.

The chemical composition of the portion 307 of the untreated gas streamwhich is routed back to the combustor 312 was then calculated. Theresults of this calculation are shown in Table 3.

TABLE 3 Stream Gas to Air Condenser Recycle Exhaust Combustor StreamKnockout Gas Gas Parameter (302) (301) (310) (307) (308) Total Flow(kg/h) 66,000 1,320,000 114,840 1,271,160 1,271,160 Temperature (° C.)25 25 30 30 30 Pressure (bar) 20 1.0 1.0 1.0 1.0 Component (vol %)Methane 100 0 0 0 0 Oxygen 0 79.0 0 3.2 3.2 Nitrogen 0 21.0 0 83.0 83.0Carbon Dioxide 0 0 0 9.5 9.5 Water 0 0 100 4.3 4.3

The gas 307 that is recycled to the combustor contains a higherconcentration of carbon dioxide, at 9.5 vol %, than the exhaust gas inExample 1, above. The recycle gas 307 also contains 3.2 vol % oxygen.The effect of recycling part of the exhaust stream 308 is to produce avent gas containing an undesirably high level of carbon dioxide, at 9.5vol %. Emitting such flue gas to the atmosphere would release over 4,000ton/day of carbon dioxide.

Example 3 Process of the Invention

The calculations for this Example were performed using the flow schemeshown in FIG. 1 and described in the Detailed Description, above. Thisflow scheme includes a sweep-based membrane separation step 111, whichwas assumed to be carried out using membranes having the permeationproperties listed in Table 1. In this calculation, stream 105 leavingthe combustor was at a pressure of 3 bar, which facilitated theoperation of the membrane sweep and the carbon dioxide capture step.

To facilitate operation of the calculation software, for Examples 3through 7, the base case air flow provided to the combustor via themembrane permeate side was assumed to be about 975 m³/h (1,250 kg/h),compared with the typical air flow to a 500 MW power plant of about 1.8million m³/h used for the calculations of Examples 1 and 2. In otherwords, the scale of the calculation for the following Examples was about1/1,200 of the scale for a typical natural gas-fired power plant. Thisreduces membrane area proportionately, but does not affect the relativeflow rates or compositions of the streams involved. The results of thiscalculation are shown in Table 3, below.

The membrane area was assumed to be 550 m², and the combustion exhauststream split ratio was set at 1:7 (flow to carbon dioxide capturestep:flow to sweep-based membrane separation step). Air flow 101 to thecombustor was assumed to be 1,250 kg/h, about the same as in Example 2.The results of this calculation are shown in Table 4.

TABLE 4 Stream Stream to Carbon Dioxide Membrane Air Gas to TreatedMethane Capture Feed Stream Combustor Exhaust Gas (102) (107) (108)(101) (103) (109) Parameter Total Flow (kg/h) 55 298 1,790 1,250 2,154885 Temperature (° C.) 25 30 30 25 29 25 Pressure (bar) 20 3.0 3.0 1.01.0 3.0 Component (vol %) Methane 100 0 0 0 0 0 Oxygen 0 3.4 3.4 79.013.7 6.2 Nitrogen 0 60.3 60.3 21.0 57.3 92.8 Carbon Dioxide 0 34.9 34.90 27.9 1.0 Water 0 1.4 1.4 0 1.2 0

In this example, the treated exhaust gases at a pressure of 3 bar aredischarged to the atmosphere. However, one or both of these gas streamscould be expanded through a turbo-expander unit to recover some of thepower used in the combustion operation, for example, to compress stream104 to the pressure required by the combustion process.

Compared with the “no membrane” Examples 1 and 2, the carbon dioxidecontent in the combustion exhaust stream (membrane feed) 108 is greatlyelevated at 34.9 vol %. The oxygen content of the combustion exhauststream 108 is 3.4 vol %. The carbon dioxide content of the treated fluegas 109 is reduced to a very low level of 1.0 vol %. Venting of a streamof this composition to the atmosphere would release only 400 ton/day ofcarbon dioxide from a 500 MW power plant. Comparing this example withExamples 1 and 2, it can be seen that the process is effective incapturing 90% of the carbon dioxide emitted from the combustion sectionof the power plant.

Example 4 Treatment of Flue Gas from Combined Cycle Gas-fired Plant byAmine Scrubbing Only (not in Accordance with the Invention)

A computer calculation was performed to determine the chemicalcomposition of exhaust gas from a natural gas combustion process, wherean amine-based carbon dioxide capture step is performed, but nosweep-based membrane separation step is used. It was assumed that aportion of the exhaust gas from the combustor was recirculated to thecombustion step as a diluent for temperature control. FIG. 4 is aschematic drawing of a flow scheme for such a combustion process.

Referring to FIG. 4, natural gas 403 and air stream 404 are introducedinto combustion step or zone 412. Stream 404 is made up of recycledexhaust stream 402 and additional air or oxygen supply stream 415.

Combustion exhaust stream 405 is withdrawn, then routed through acondenser 414, where water 407 is knocked out of the stream. Thedehydrated exhaust stream 406 is then routed to a splitter 408, fromwhich a first portion 409 of the exhaust stream is routed to an aminescrubbing plant 410, where carbon dioxide-rich stream 411 is withdrawn,and carbon dioxide-depleted stream 413 is routed to the environment astreated flue gas. The other portion 402 of the exhaust stream is routedback to the combustor 412 as stream 402. In this example, the splitratio was 3:2, meaning that 60 vol % of the exhaust stream was routed tothe amine-based carbon dioxide capture step 410 and the remaining 40 vol% of the exhaust stream was routed back to the combustor 412.

The chemical composition of the gas stream 402 which is routed back tothe combustor 412 was then calculated. The results of this calculationare shown in Table 5.

TABLE 5 Stream CO₂ Vent Gas Gas to Flue Amine Concentrate From AirCombustor Methane Gas Plant Feed Stream Amine Unit (415) (402) (403)(406) (409) (411) (413) Parameter Total Flow (kg/h) 1,250 800 55 2,0131,213 151 1,062 Temperature (° C.) 25 30 25 30 30 30 30 Pressure (bar)1.0 1.0 10.0 1.0 1.0 1.0 1.0 Component (vol %) Methane 0 0 100 0 0 0 0Oxygen 21.0 5.4 0 5.4 5.4 0.6 5.8 Nitrogen 79.0 82.1 0 82.1 82.1 1.089.5 Carbon Dioxide 0 8.2 0 8.2 8.2 98.2 0.09 Water 0 4.3 0 4.3 4.3 0.24.6

The carbon dioxide-rich stream 411 withdrawn from the amine scrubbingstep 410 contains a carbon dioxide concentration of 98.2 vol %, andrecovers essentially all of the carbon dioxide from the combustor. Thegas stream 402 that is recycled to the combustor contains 8.2 vol %carbon dioxide and 5.4 vol % oxygen concentration.

Example 5 Process of the Invention Treating Flue Gas from Combined CycleGas-fired Plant

The calculations for this Example were performed using the flow schemeshown in FIG. 1 and described in the Detailed Description, above. Thisflow scheme includes an amine scrubbing step 113 performed in parallelwith a sweep-based membrane separation step 111.

In this set of calculations, the membrane area was assumed to be 2,800m², and the combustion exhaust stream split was set at 1:5 (flow tocarbon dioxide capture step:flow to sweep-based membrane separationstep), these parameters being set to achieve about 90 vol % carbondioxide recovery. Air flow 101 is 1,250 kg/h. The results of thiscalculation are shown in Table 6.

TABLE 6 Stream Vent Gas Membrane Gas to Amine CO₂ Conc. From MembraneResidue Treated Air Combustor Methane Plant Feed Stream Amine Unit FeedFlue Gas (115) (103) (102) (107) (117) (119) (108) (109) Parameter TotalFlow (kg/h) 1,250 1,884 55 304 129 175 1,520 864 Temperature (° C.) 2529 25 30 30 30 30 25 Pressure (bar) 1.0 1.0 10.0 1.0 1.0 1.0 1.0 1.0Component (vol %) Methane 0 0 100 0 0 0 0 0 Oxygen 21.0 12.3 0 7.1 0.021.0 7.1 6.1 Nitrogen 79.0 59.9 0 63.1 0.2 92.3 63.1 92.8 Carbon Dioxide0 24.4 0 31.9 99.7 0.5 31.9 1.2 Water 0 0.3 0 4.3 0.04 6.2 4.3 0

The carbon dioxide-rich stream 117 from the amine scrubbing stepcontains 99.7 vol % carbon dioxide. The stream 103 that is routed backto the combustor contains relatively high concentrations of both carbondioxide and oxygen, at 24.4 and 12.3 vol %, respectively. The flue gas109 that is released to the environment contains 1.2 vol % carbondioxide.

The concentration of carbon dioxide in the feed stream to the amine unitis about 32 vol %, compared with only 8 vol % in Example 4. The flow ofgas routed to the amine plant is cut to from about 1,200 kg/h to 304kg/h, which would cut the required capacity of the amine plant to abouta quarter of the corresponding prior art requirement.

Example 6 Treatment of Flue Gas from Combined Cycle Gas-fired Plant byAmine Scrubbing at Pressure (not in Accordance with the Invention)

A computer calculation was performed to determine the chemicalcomposition of exhaust gas from a natural gas combustion process, wherean amine-based carbon dioxide capture step is performed, but nosweep-based membrane separation step is used. The calculation differsfrom that of Example 4 in that the exhaust gas was assumed to becompressed to 10 bar before being routed to the amine scrubbing plant.In a combined cycle plant, the air coming into the combustor is normallycompressed to high pressure, such as 10 bar or more. Compressing theexhaust gas means that diluent gas diverted from the flue gas stream tobe recycled to the combustor will be at high pressure, and may bereturned without recompression, thereby saving on the compressorcapacity used in the combustion/power generation steps. The amine plantis also operated at pressure. FIG. 5 is a schematic drawing of a flowscheme for such a combustion process.

Referring to FIG. 5, natural gas 503 and air stream 504 are introducedinto combustion step or zone 512. Stream 504 is made up of recycledexhaust stream 502 and additional air or oxygen supply stream 515.

Combustion exhaust stream 505 is withdrawn, then routed through acondenser 514, where water 507 is knocked out of the stream. Thedehydrated exhaust stream 506 is then routed to a compressor 508, whereit is compressed to 10 bar. The compressed exhaust stream 510 passesthrough aftercooler/separator 511, yielding water stream, 521, andcompressed stream, 513. Stream 513 then passes to splitter 516, fromwhich a first portion 517 of the exhaust stream is routed to an aminescrubbing plant 518, which operates under pressure to produce carbondioxide-rich stream 519, which is withdrawn, and compressednitrogen-rich off-gas stream, 520. This stream remains at pressure andis routed to turbo-expander, 522, which is linked in power-transferringrelationship to compressor, 508. A substantial portion of the powerrequired to drive compressor 508 can be generated in this way.

The other portion 502 of the exhaust stream is routed back to thecombustor 512 as stream 502. This stream remains at 10 bar, so it can bereturned at essentially this pressure to the combined cyclecombustion/power generation step. In this example, 60 vol % of theexhaust stream was routed to the amine scrubbing step, 518, and theremaining 40 vol % of the exhaust stream was routed back to thecombustor 512.

The chemical composition of the gas stream 502 which is routed back tothe combustor 512 was then calculated. The results of this calculationare shown in Table 7.

TABLE 7 Stream CO₂ Vent Gas Gas to Flue Amine Concentrate From AirCombustor Methane Gas Plant Feed Stream Amine Unit (515) (502) (503)(506) (517) (519) (520) Parameter Total Flow (kg/h) 1,250 800 55 2,0131,213 151 1,062 Temperature (° C.) 25 30 25 30 30 30 30 Pressure (bar)1.0 10.0 10.0 1.0 10.0 1.0 10.0 Component (vol %) Methane 0 0 100 0 0 00 Oxygen 21.0 5.4 0 5.4 5.4 0.6 5.8 Nitrogen 79.0 82.1 0 82.1 82.1 1.089.5 Carbon Dioxide 0 8.2 0 8.2 8.2 98.2 0.09 Water 0 4.3 0 4.3 4.3 0.24.6

The carbon dioxide-rich stream 519 withdrawn from the amine scrubbingstep 518 contains a carbon dioxide concentration of 98.2 vol %. The gasstream 502 that is recycled to the combustor contains a relatively lowconcentration of carbon dioxide at 8.2 vol %, and an oxygenconcentration of 5.4 vol %.

Example 7 Process of the Invention Treating Flue Gas from Combined CycleGas-fired Plant at Pressure

A computer calculation was performed to determine the chemicalcomposition of exhaust gas from a natural gas combustion process, wherean amine-based carbon dioxide capture step and sweep-based membraneseparation step are performed in parallel. The calculation differs fromthat of Example 5 in that the exhaust gas was assumed to be compressedto 10 bar, as in Example 6. FIG. 6 is a schematic drawing of a flowscheme for such a combustion process.

Referring to FIG. 6, natural gas 603 and air stream 604 are introducedinto combustion step or zone 612. Stream 604 is made up of recycledexhaust stream 602 and additional air or oxygen supply stream 615.

Combustion exhaust stream 605 is withdrawn, then routed through acondenser 614, where water 607 is knocked out of the stream. Thedehydrated exhaust stream 606 is then routed to a compressor 608, whereit is compressed to 10 bar. The compressed exhaust stream 610 passesthrough aftercooler/separator 611, yielding water stream 625. Stream 613passes to splitter 616, from which a first portion 617 of the exhauststream is routed to an amine scrubbing plant 618, which operates underpressure to produce carbon dioxide-rich stream 619, which is withdrawn,and compressed nitrogen-rich off-gas stream, 620. This stream remains atpressure and is routed, via line 628, to turbo-expander, 626, which islinked in power-transferring relationship to compressor, 608. Asubstantial portion of the power required to drive compressor 608 can begenerated in this way.

The other portion 621 of the exhaust stream is routed to a sweep-basedmembrane separation step 622. Membrane unit 622 contains membranes 623which exhibit a high permeance for carbon dioxide, as well as highselectivity for carbon dioxide over nitrogen. The compressed, condensedexhaust stream 621 flows across the feed side of the membranes; a sweepgas of air, 601 flows across the permeate side. The sweep stream picksup the preferentially permeating carbon dioxide, and the resultingpermeate stream 602 is withdrawn from the membrane unit and is combinedwith stream 615 to form the air or oxygen feed 604 to the combustor. Thenitrogen-rich exhaust stream 624 from the membrane separation step 622remains at pressure and is combined with the off-gas stream 620 from theamine scrubbing step to form stream 628, which is then routed to theturbo-expander, 626, to provide power to drive compressor 608. Theresulting treated flue gas stream 627 is released to the environment.

In this example, about 17 vol % of the exhaust stream was routed to theamine-based carbon dioxide capture step 618 and the remaining 83 vol %of the exhaust stream was routed to the sweep-based membrane separationstep 622.

The chemical composition of the gas stream 602 which is routed back tothe combustor 612 was then calculated. The results of this calculationare shown in Table 8.

TABLE 8 Stream Vent Gas Membrane Gas to Amine CO₂ Conc. From MembraneResidue Treated Air Combustor Methane Plant Feed Stream Amine Unit FeedFlue Gas (601) (602) (603) (617) (619) (620) (621) (624) Parameter TotalFlow (kg/h) 1,250 2,163 55 349 148 202 1,746 833 Temperature (° C.) 2527 25 30 30 30 30 25 Pressure (bar) 1.0 1.0 10.0 10.0 10.0 10.0 10.010.0 Component (vol %) Methane 0 0 100 0 0 0 0 0 Oxygen 0 14.5 0 4.4 0.26.4 4.4 6.0 Nitrogen 79.0 59.7 0 62.9 0.2 92.5 62.9 93.8 Carbon Dioxide21.0 25.4 0 32.2 99.7 0.5 32.2 0.13 Water 0 0.4 0 0.4 0 0.7 4.5 0

The carbon dioxide-rich stream 619 from the amine scrubbing stepcontains 99.7 vol % carbon dioxide. The stream 602 that is routed backto the combustor contains relatively high concentrations of both carbondioxide and oxygen, at 25.4 and 14.5 vol %, respectively. The flue gas627 that is released to the environment—which is a combination ofstreams 620 and 624—contains 0.2 vol % carbon dioxide.

The concentration of carbon dioxide in the feed stream to the amine unitis about 32 vol %, compared with only 8 vol % in Example 6. The flow ofgas routed to the amine plant is cut to from about 1,200 kg/h to 349kg/h, which would cut the required capacity of the amine plant toslightly more than a quarter of the corresponding prior art requirement.

Example 8 Combustion Process with Parallel Carbon Capture andSweep-based Membrane Separation Steps According to FIG. 7

A computer calculation was performed to determine the chemicalcomposition of exhaust gas from a natural gas combustion process, wherea membrane-based carbon dioxide capture step and sweep-based membraneseparation step are performed in parallel. The exhaust gas was assumedto be compressed to 5 bar. It was further assumed that the engine (orboiler) of the combustion step produces about 1 ton/h of CO₂ in itsexhaust gas and about 2-2.5 MW of power as electricity (or about 5 MW ofpower as steam). FIG. 7 is a schematic drawing of a flow scheme for sucha combustion process.

Referring to FIG. 7, natural gas 703 and air stream 704 are introducedinto combustion step or zone 712. Stream 704 is made up of recycledexhaust stream 702 and additional air or oxygen supply stream 715.

Combustion exhaust stream 705 is withdrawn, and passed through a heatexchanger, 732. This exhaust gas is often quite hot, typically in therange of 100-200° C. The gas is cooled in unit 732 to produce cooledstream 733. This stream is then routed through a condenser 714, wherewater 707 is knocked out. The dehydrated exhaust stream, 706, is thenrouted to a compressor, 708, where it is compressed to 5 bar. Thecompressed exhaust stream, 710, passes through aftercooler/separator711, yielding water stream 725. Stream 713 passes to splitter 716, fromwhich a first portion 717 of the exhaust stream (about ⅓) is routed to amembrane separation carbon dioxide capture step 718. The membrane ofstep 718 contains membrane(s) 729 which exhibit a high permeance forcarbon dioxide, as well as high selectivity for carbon dioxide overnitrogen. Accordingly, step 718 produces a permeate stream, 719,enriched in carbon dioxide as compared to the feed stream 717 and acarbon dioxide-depleted, nitrogen-rich residue stream, 720.

Permeate stream 719 is withdrawn from step 718 using a vacuum pump, 730,which produces a carbon dioxide concentrated stream, 731. This streamcan be further compressed, condensed and purified to produce liquid,high pressure carbon dioxide suitable for many uses. The energy cost ofthe operation is about 100 KW. Residue stream 720 remains at pressureand is eventually routed, via lines 728 and 734 (discussed below), to aturbo-expander, 726, which is linked in power-transferring relationshipto compressor 708. A substantial portion of the power required to drivecompressor 708 can be generated in this way.

The other/second portion of the exhaust stream, 721, is routed to asweep-based membrane separation step 722. Membrane or membranes 723exhibit a high permeance for carbon dioxide, as well as high selectivityfor carbon dioxide over nitrogen. The compressed, condensed exhauststream 721 flows across the feed side of the membranes; a sweep gas ofair, 701 flows across the permeate side. The sweep stream picks up thepreferentially permeating carbon dioxide, and the resulting permeatestream 702 is withdrawn from the membrane unit and is combined withstream 715 to form the air or oxygen feed 704 to the combustor. Thenitrogen-rich exhaust stream 724 from the membrane separation step 722remains at pressure and is, in this example, combined with the residuestream from step 718 to form a working gas/mixed gas stream 728. Thisstream undergoes a heat exchange against the hot exhaust stream 705 inheat exchanger 732, which produces a warmed stream 734. Warmed stream734 is then routed to the turbo-expander, 726, to provide power to drivecompressor 708. The resulting treated flue gas stream 727 is released tothe environment.

Using stream 728 going to the turbo expander, 726, to help cool stream705 going to compressor 708 is beneficial. The energy cost ofcompression is lower when the gas being compressed is cool.Correspondingly, the energy recovered in a turbo expander is higher whenthe gas being expanded is warm.

In this example, about 30 vol % of the exhaust stream was routed to themembrane-based carbon dioxide capture step 718 and the remaining 70 vol% of the exhaust stream was routed to the sweep-based membraneseparation step 722.

The chemical composition of the gas stream 702 which is routed back tothe combustor 712 was then calculated. The results of this calculationare shown in Table 9.

TABLE 9 Stream Sweep-based Compressed/ Membrane Released Gas to ExhaustCondensed CO₂ Conc. First Membrane Residue Treated Treated Air CombustorGas Exhaust Stream Stream Residue Stream Flue Gas Flue Gas (701) (702)(705) (721) (731) (720) (724) (727) Parameter Total Flow (kg/h) 7,2809,580 9,950 6,410 810 1,940 4,110 6,050 Temperature (° C.) 30 50 150 60230 60 30 13 Pressure (bar) 1.0 1.0 1.0 5.0 1.0 5.0 5.0 1.0 Component(vol %) Methane 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Oxygen 21.0 16.8 2.1 2.41.4 2.8 3.7 3.4 Nitrogen 79.0 69.8 65.2 74.8 23.5 91.2 93.1 92.5 CarbonDioxide 0.0 12.1 18.0 20.7 66.9 6.0 3.2 4.1 Water 0.0 1.3 14.7 2.1 8.20.0 0.0 0.0

The carbon dioxide-rich stream 731 from the membrane-based carbondioxide capture step 718 contains about 67% of carbon dioxide (about 73vol % on a dry basis). The stream 702 that is routed back to thecombustor contains relatively high concentrations of both carbon dioxideand oxygen, at 12.1 and 16.8 vol %, respectively. The flue gas 727 thatis released to the environment—which is a combination of streams 720 and724—contains 4.1 vol % carbon dioxide.

The total process uses about 310 KW in the turbo compressor/expander andanother 40 KW in the vacuum pump. Another 100 KW is used tocondense/liquefy/purify the carbon dioxide in stream 731, so the totalenergy use is about 450 KW or about 20% of the power produced by theengine. The system captures about 63% of the carbon dioxide produced bythe plant.

Example 9 Combustion Process with Parallel Carbon Capture andSweep-based Membrane Separation Steps According to FIG. 8

A computer calculation was performed to determine the chemicalcomposition of exhaust gas from a natural gas combustion process, wherea two-step membrane-based carbon dioxide capture step and sweep-basedmembrane separation step are performed in parallel. The exhaust gas wasassumed to be compressed to 5 bar. It was further assumed that theengine (or boiler) of the combustion step produces about 1 ton/h of CO₂in its exhaust gas and about 2 MW of power as electricity (or about 5 MWof power as steam). FIG. 8 is a schematic drawing of a flow scheme forsuch a combustion process.

Referring to FIG. 8, natural gas 803 and air stream 804 are introducedinto combustion step or zone 812. Stream 804 is made up of recycledexhaust stream 802 and additional air or oxygen supply stream 815.

Combustion exhaust stream 805 is withdrawn and passed through a heatexchanger, 834, where it is cooled to produce cooled stream 836. Thisstream is then routed through a condenser, 814, where water 807 isknocked out. The dehydrated exhaust stream 806 is then routed to acompressor, 808, where it is compressed to 5 bar. The compressed exhauststream, 810, passes through aftercooler/separator 811, yielding waterstream 825. Stream 813 passes to splitter 816, from which a firstportion 817 of the exhaust stream is routed to a two-step membraneseparation carbon dioxide capture step, 818 a-b. Step 818 a-b containsmembranes 829 a-b, which exhibit a high permeance for carbon dioxide, aswell as high selectivity for carbon dioxide over nitrogen.

In step 818 a, a first permeate stream, 819, enriched in carbon dioxideas compared to feed stream 817, is withdrawn using a vacuum pump, 830,which produces a carbon dioxide concentrated stream, 831. This streamcan be further compressed, condensed and purified to produce liquid,high pressure carbon dioxide suitable for many uses. The energy cost ofthe operation is about 100 KW. First residue stream 832 remains atpressure and is routed as a feed stream to step 818 b.

In step 818 b, a second permeate stream, 833, enriched in carbon dioxidecompared to stream 832, is sent back to the combustor step 812 as partof the recycled exhaust stream 802. A second residue stream, 820,remains at pressure and is routed, via lines 828 and 835 (discussedbelow), to a turbo-expander, 826, which is linked in power-transferringrelationship to compressor 808. A substantial portion of the powerrequired to drive compressor 808 can be generated in this way.

The other/second portion of the exhaust stream, 821, is routed to asweep-based membrane separation step 822. Membrane or membranes 823exhibit a high permeance for carbon dioxide, as well as high selectivityfor carbon dioxide over nitrogen. The compressed, condensed exhauststream 821 flows across the feed side of the membranes; a sweep gas ofair, 801 flows across the permeate side. The sweep stream picks up thepreferentially permeating carbon dioxide, and the resulting permeatestream 802 is withdrawn from the membrane unit and is combined withstreams 815 and 833 to form the air or oxygen feed, 804, to thecombustor. The nitrogen-rich exhaust stream 824 from the membraneseparation step 822 remains at pressure and is combined with the secondresidue stream, 820, to form working gas/mixed stream 828. This streamundergoes a heat exchange against the hot exhaust stream 805 in heatexchanger 834, which produces a warmed stream 835. Warmed stream 835 isthen routed to the turbo-expander, 826, to provide power to drivecompressor 808. The resulting treated flue gas stream 827 is released tothe environment.

In this example, about 30 vol % of the exhaust stream was routed to thetwo-step membrane-based carbon dioxide capture step 818 a-b and theremaining 70 vol % of the exhaust stream was routed to the sweep-basedmembrane separation step 822.

The chemical composition of the gas stream 802, which is routed back tothe combustor 812, was then calculated. The results of this calculationare shown in Table 10.

TABLE 10 Stream Sweep-based Compressed/ Membrane First Membrane Gas toExhaust Condensed Residue Treated Permeate CO₂ Conc. Air Combustor GasExhaust Stream Flue Gas Stream Stream (801) (802) (805) (821) (824)(819) (831) Parameter Total Flow (kg/h) 7,280 9,695 10,776 6,994 4,579886 887 Temperature (° C.) 30 51 150 60 30.0 60 234 Pressure (bar) 1.01.0 1.0 5.0 5.0 0.2 1.0 Component (vol %) Methane 0.0 0.0 0.0 0.0 0.00.0 0.0 Oxygen 21.0 16.6 2.2 2.5 3.8 1.5 1.5 Nitrogen 79.0 69.2 65.774.6 92.3 23.3 23.3 Carbon Dioxide 0.0 12.8 18.4 20.9 3.8 67.0 67.0Water 0.0 1.4 13.7 2.0 0.1 8.2 8.2 Stream Working Released FirstMembrane Second Membrane Second Membrane Gas/Mixed Treated ResidueStream Residue Stream Residue Stream Gas Stream Flue Gas (832) (833)(820) (828) (827) Parameter Total Flow (kg/h) 2,110 715 1,395 5,9745,974 Temperature (° C.) 59 60 59 37 12 Pressure (bar) 5.0 1.0 5.0 5.01.0 Component (vol %) Methane 0.0 0.0 0.0 0.0 0.0 Oxygen 2.9 3.9 2.4 3.43.4 Nitrogen 91.1 81.6 95.6 93.1 93.1 Carbon Dioxide 6.0 14.4 2.0 3.43.4 Water 0.0 0.1 0.0 0.1 0.1

The carbon dioxide-rich stream 819 from the membrane-based carbondioxide capture step 818 contains about 67% of carbon dioxide (about 73vol % on a dry basis). The stream 802 that is routed back to thecombustor contains relatively high concentrations of both carbon dioxideand oxygen, at 12.8 and 16.6 vol %, respectively. The flue gas 827 thatis released to the environment—which is a combination of streams 820 and824—contains 3.4 vol % carbon dioxide.

The total process uses about 450 KW or about 20% of the power producedby the engine. The system captures about 70% of the carbon dioxideproduced by the plant.

We claim:
 1. A process for controlling carbon dioxide exhaust from acombustion process, comprising: (a) combusting a mixture comprising afuel and air, oxygen-enriched air, or oxygen in a combustion apparatus,thereby creating an exhaust stream comprising carbon dioxide andnitrogen; (b) routing the exhaust stream to a compression apparatus tocompress the exhaust stream, thereby producing a compressed stream; (c)separating a first portion of the compressed stream in a carbon dioxidecapture unit adapted to selectively remove carbon dioxide, therebyproducing a carbon dioxide-enriched stream and a carbon dioxide-depletedoff-gas stream; (d) providing a membrane having a feed side and apermeate side, and being selectively permeable to carbon dioxide overthe nitrogen and to carbon dioxide over oxygen; (e) passing a secondportion of the compressed stream across the feed side; (f) passing air,oxygen-enriched air, or oxygen as a sweep stream across the permeateside; (g) withdrawing from the feed side a carbon dioxide-depletedresidue stream; (h) withdrawing from the permeate side a permeate streamcomprising oxygen and carbon dioxide; (i) passing the permeate stream tostep (a) as at least part of the air, oxygen-enriched air, or oxygenused in step (a); and (j) routing the carbon dioxide-depleted off-gasstream from step (c) and the carbon dioxide-depleted residue stream fromstep (g) as a part of a working gas stream to an expander unit, andoperating the expander unit, thereby generating power and producing avent stream.
 2. The process of claim 1, wherein the combustion apparatusis selected from the group consisting of a boiler, a furnace, an oven, agas turbine, and a gas-powered or a diesel-powered engine.
 3. Theprocess of claim 2, wherein the combustion apparatus is a gas-powered ora diesel-powered engine.
 4. The process of claim 1, wherein the exhauststream comprises at least 15 vol % CO₂.
 5. The process of claim 1,wherein the first portion of the compressed stream comprises betweenabout 10 vol % and about 66 vol % of the compressed stream.
 6. Theprocess of claim 5, wherein the first portion of the compressed streamcomprises between about 20 vol % and about 50 vol % of the compressedstream.
 7. The process of claim 6, wherein the first portion of thecompressed stream comprises between about 25 vol % and about 35 vol % ofthe compressed stream.
 8. The process of claim 1, wherein the carbondioxide capture unit comprises at least one process selected from thegroup consisting of absorption, adsorption, liquefaction and membraneseparation.
 9. The process of claim 8, wherein the carbon dioxidecapture step comprises amine scrubbing.
 10. The process of claim 8,wherein the carbon dioxide capture step comprises membrane separation.11. The process of claim 10, wherein the carbon dioxide capture stepcomprises two or more membrane separation steps.
 12. The process ofclaim 1, wherein the exhaust stream is compressed to a pressure of up toabout 5 bar in step (b).
 13. The process of claim 1, wherein the sweepstream follows a sweep flow direction across the permeate side, thesecond portion of the compressed stream follows a feed flow directionacross the feed side, and the sweep flow direction is substantiallycountercurrent to the feed flow direction.
 14. The process of claim 1,wherein the membrane exhibits a carbon dioxide permeance of at least 500gpu under process operating conditions.
 15. The process of claim 1,wherein the membrane exhibits a selectivity in favor of carbon dioxideover nitrogen of at least 10 under process operating conditions.
 16. Theprocess of claim 1, wherein the vent stream comprises 5 vol % carbondioxide or less.
 17. The process of claim 1, wherein the expander unitis a turbo expander mechanically linked to the compression apparatus.18. The process of claim 1, further comprising the step of routing theexhaust stream from step (a) to a condensation unit, thereby producing awater stream, prior to step (b).
 19. The process of claims 1 or 18,further comprising the step of routing the compressed stream from step(b) to a condensation unit or a second condensation unit, respectively,thereby producing a water or second water stream, prior to steps (c) and(e).
 20. The process of claim 11, wherein a permeate stream from asecond or additional membrane separation step in step (c) is passed asat least part of the air, oxygen-enriched air, or oxygen used in step(a).
 21. The process of claim 1, wherein the carbon dioxide-enrichedstream comprises at least 60 vol % CO₂.
 22. A process for controllingcarbon dioxide exhaust from a combustion process, comprising: (a)combusting a mixture comprising a fuel and air, oxygen-enriched air, oroxygen in a combustion apparatus, thereby creating an exhaust streamcomprising carbon dioxide and nitrogen; (b) routing the exhaust streamto a compression apparatus to compress the exhaust stream, therebyproducing a compressed stream; (c) separating a first portion of thecompressed stream in a carbon dioxide capture, unit adapted toselectively remove carbon dioxide, thereby producing a carbondioxide-enriched stream and a carbon dioxide-depleted off-gas stream;(d) providing a membrane having a feed side and a permeate side, andbeing selectively permeable to carbon dioxide over nitrogen and tocarbon dioxide over oxygen; (e) passing a second portion of thecompressed stream across the feed side; (f) passing air, oxygen-enrichedair, or oxygen as a sweep stream across the permeate side; (g)withdrawing from the feed side a carbon dioxide-depleted residue stream;(h) withdrawing from the permeate side a permeate stream comprisingoxygen and carbon dioxide; (i) passing the permeate stream to step (a)as at least part of the air, oxygen-enriched air, or oxygen used in step(a); and (j) routing at least one of the carbon dioxide-depleted off-gasstream from step (c) or the carbon dioxide-depleted residue stream fromstep (g) as a part of a working gas stream to an expander unit, andoperating the expander unit, thereby generating power and producing avent stream, wherein the exhaust gas from the combustion apparatus iscooled prior to compression by heat exchange with at least a portion ofthe working gas stream being routed to the expander unit in step (j).